US4417038A - Ethylene-alkyne copolymers, their preparation and their use as additives to petroleum distillates - Google Patents

Ethylene-alkyne copolymers, their preparation and their use as additives to petroleum distillates Download PDF

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Publication number
US4417038A
US4417038A US06/327,727 US32772781A US4417038A US 4417038 A US4417038 A US 4417038A US 32772781 A US32772781 A US 32772781A US 4417038 A US4417038 A US 4417038A
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United States
Prior art keywords
ethylene
copolymers
weight
terpolymers
percent
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Expired - Fee Related
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US06/327,727
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Inventor
Hans-Henning Vogel
Manfred Schramm
Michael Werner
Erich Schwartz
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BASF SE
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BASF SE
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Assigned to BASF AKTIENGESELLSCHAFT, 6700 LUDWIGSHAFEN, RHEINLAND-PFALZ, GERMANY, reassignment BASF AKTIENGESELLSCHAFT, 6700 LUDWIGSHAFEN, RHEINLAND-PFALZ, GERMANY, ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SCHRAMM, MANFRED, SCHWARTZ, ERICH, VOGEL, HANS-HENNING, WERNER, MICHAEL
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic

Definitions

  • the present invention relates to ethylene-alkyne copolymers and ethylene-alkyne-alkene terpolymers, their preparation and their use as additives to petroleum distillates.
  • Copolymers for the above purpose require on the one hand to be very effective in improving the low-temperature properties of petroleum distillates whilst on the other hand they must be obtainable by a sufficiently simple process.
  • the ethylene/vinylcarboxylic acid ester copolymers and terpolymers conventionally used in petroleum distillates have the disadvantage that they are not equally effective in all petroleum distillates. Rather, the effect of the conventional additives depends, inter alia, greatly on the origin of the crude oil from which the distillate is derived, on the method of processing of the crude oil and on the nature and amount of n-paraffin hydrocarbons in the petroleum distillate, i.e., for example, on the boiling range or boiling point of the distillate.
  • ethylene-alkyne copolymers which have a number-average molecular weight, determined by vapor phase osmometry, of from 500 to 500,000, preferably from 500 to 10,000, especially from 1,000 to 5,000, and which contain, as copolymerized units, (A) from 70 to 99 percent by weight of ethylene, based on copolymer, and (B) an acetylenically unsaturated compound of the general formula (I)
  • R 1 is (OCH 2 CH 2 ) n H or CH 2 --R 2 , n is 1 -20, R 2 is --OH, --OCOR 3 or --COOR 3 and R 3 is straight-chain or branched C 1 -C 10 -alkyl.
  • Preferred copolymers are ternary ethylene-alkyne-alkene copolymers which contain, as copolymerized units, from 50 to 99 percent by weight of (A), from 0.5 to 30 percent by weight of (B) and, in addition, (C) from 0.5 to 49.5 percent by weight of an olefinically unsaturated ester of the general formula (II) ##STR2## where R 4 is H or CH 3 , R 5 is --OOC--R 6 or --COOR 6 and R 6 is straight-chain or branched C 1 -C 10 -alkyl or hydrogen, the sum of the percentages by weight of (A), (B) and (C) is 100.
  • Another object of the invention is achieved by a process for the preparation of the ethylene-alkyne copolymers described at the outset, wherein the copolymerization of ethylene with an acetylenically unsaturated compound of the general formula I, with or without an olefinically unsaturated ester of the general formula II, is carried out in a continuous or batchwise polymerization system at from 150° to 350° C. under a pressure of from 500 to 3,000 bar in the presence of from 200 to 4,000 mole ppm, based on monomers, of an organic peroxide which decomposes into free radicals, in the presence or absence of oxygen and in the presence or absence of a polymerization regulator.
  • the novel ethylene-alkyne copolymers and ethylene-alkyne-alkene terpolymers are solid or waxy substances (depending on the molecular weight), which still contain double bonds.
  • the copolymers have a number-average molecular weight, determined by vapor phase osmometry, of from 500 to 500,000, preferably from 500 to 10,000. Copolymers with average molecular weights of from 1,000 to 5,000 are particularly suitable for use in petroleum distillates.
  • the copolymers according to the invention contain from 70 to 99 percent by weight of ethylene, based on copolymer, together with an acetylenically unsaturated compound of the general formula H--C.tbd.C--R 1 (I), where R 1 is H(OCH 2 CH 2 ) n or CH 2 --R 2 , n is 1-20, R 2 is --OH, --OCOR 3 or --COOR 3 and R 3 is straight-chain or branched C 1 -C 10 -alkyl.
  • the unsaturated compound of the formula I are prop-1-ynyl acetate, prop-1-ynol, methoxybut-1-yne and acetylene, amongst which the first-mentioned is particularly suitable.
  • the content of the acetylenically unsaturated compound (I) in the copolymer is from 0.5 to 30 percent by weight, based on copolymer.
  • Preferred copolymers are terpolymers which contain, as copolymerized units, 65-98 percent by weight of ethylene, 1-20 percent by weight of the acetylenically unsaturated compound (I) and 1-34 percent by weight of a third component, namely an olefinically unsaturated ester of the general formula (II) ##STR3## where R 4 is H or CH 3 , R 5 is OOC--R 6 or COOR 6 and R 6 is straight-chain or branched C 1 -C 10 -alkyl or hydrogen, and the sum of the percentages by weight of (A), (B) and (C) is 100.
  • Examples of the olefinically unsaturated compound of the formula (II) are vinyl esters, e.g. vinyl acetate, and acrylic acid esters, e.g. ethylhexyl acrylate and n-butyl acrylate. Vinyl acetate is particularly suitable as the third comonomer.
  • Especially preferred terpolymers are those which contain, as copolymerized units, from 75 to 80 percent by weight of ethylene, from 3 to 15 percent by weight of compound (I) and from 5 to 22 percent by weight of compound (II).
  • the said copolymers and terpolymers may contain from 0.01 to 10, especially from 0.05 to 5, percent by weight, based on polymer, of monomers (I) and/or (II) which have not been converted during the polymerization or have been added subsequent to completion of the polymerization.
  • the ethylene-alkyne copolymers or terpolymers are prepared by copolymerizing ethylene with an acetylenically unsaturated compound of the general formula (I), with or without an unsaturated ester of the general formula (II), in a continuous or batchwise polymerization system at from 150° to 350° C., under a pressure of from 500 to 3,000 bar, in the presence of an organic peroxide which decomposes into free radicals, and in the presence or absence of oxygen and the presence or absence of a polymerization regulator.
  • tubular reactors are tubular polymerization vessels whose length is from 10,000 to 40,000 times the diameter of the circular-section tube.
  • autoclave reactors whose inner space generally has a ratio of height to diameter of the circular cross-section of from 1:1 to 20:1, the reaction mixture is agitated by means of stirrers.
  • the process according to the invention entails copolymerization in the presence of relatively large amounts of peroxide, namely from 200 to 4,000, preferably from 400 to 3,000, more especially from 800 to 3,000, mole ppm, based on monomers.
  • peroxide namely from 200 to 4,000, preferably from 400 to 3,000, more especially from 800 to 3,000, mole ppm, based on monomers.
  • tert.-Butyl perisononanate is a particularly suitable peroxide.
  • novel ethylene copolymers are used, in an amount of from 0.001 to 2 percent by weight, as an additive to petroleum distillates of boiling range from 120 to 400° C., in order to improve the flow and/or to lower the pour point and the cold filter plugging point as defined in DIN 51,428. Moreover they are used, in an amount of from 0.001 to 2 percent by weight, as an additive for lowering the setting point of petroleum distillates (neutral oils) which have a boiling range of about 400° C., have been obtained by conventional methods, for example by vacuum distillation, and serve as starting materials for the preparation of lubricants.
  • novel ethylene copolymers are used as an additive to petroleum distillates which have been obtained by vacuum distillation and serve as starting materials for the preparation of lubricating oils, the additives being intended to improve the low-temperature properties (setting point and pour point and/or cold filter plugging point).
  • the novel copolymers and terpolymers, prepared according to the invention may contain small amounts of relatively high molecular weight polymerization products which can be kept in solution, advantageously by the measures described in German Laid-Open application DOS No. 2,832,738, when using the copolymers and terpolymers as additives to petroleum distillates.
  • the polymers contain small amounts of residual comonomers, in order to prevent premature precipitation of the relatively high molecular weight polymerization products.
  • the comonomers can also be added subsequently, individually or as a mixture, in amounts of from 0.5 to 5 percent by volume, based on the ethylene copolymer or terpolymer.
  • the comonomer content was determined by saponification and titration of the excess alkali.
  • the content of polymer was calculated from the total oxygen, with allowance for appropriate corrections found from comparative experiments.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US06/327,727 1980-12-12 1981-12-04 Ethylene-alkyne copolymers, their preparation and their use as additives to petroleum distillates Expired - Fee Related US4417038A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3046802 1980-12-12
DE19803046802 DE3046802A1 (de) 1980-12-12 1980-12-12 Ethylen-alkin-copolymerisate, deren herstellung und verwendung als zusatz zu erdoeldestillaten

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US4417038A true US4417038A (en) 1983-11-22

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US (1) US4417038A (de)
EP (1) EP0054138B1 (de)
JP (1) JPS57121011A (de)
CA (1) CA1222348A (de)
DE (2) DE3046802A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532270A (en) * 1984-01-27 1985-07-30 National Starch And Chemical Corporation High temperature stable adhesive compositions employing aromatic polyimide and polyisoimide bis-acetylene additives
US5559191A (en) * 1994-08-30 1996-09-24 Bp Chemicals Limited Functionalised hydrocarbyl polymers
US20040002739A1 (en) * 2002-06-28 2004-01-01 Cates Adam W. Method and apparatus for delivering pre-shock defibrillation therapy

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4042206A1 (de) * 1990-12-29 1992-07-02 Hoechst Ag Terpolymerisate des ethylens, ihre herstellung und ihre verwendung als additive fuer mineraloeldestillate
US6361522B1 (en) 1999-10-21 2002-03-26 Cardiac Pacemakers, Inc. Drug delivery system for implantable cardiac device
US7369890B2 (en) 2000-11-02 2008-05-06 Cardiac Pacemakers, Inc. Technique for discriminating between coordinated and uncoordinated cardiac rhythms
US6689117B2 (en) 2000-12-18 2004-02-10 Cardiac Pacemakers, Inc. Drug delivery system for implantable medical device
US7209783B2 (en) 2001-06-15 2007-04-24 Cardiac Pacemakers, Inc. Ablation stent for treating atrial fibrillation
US7493162B2 (en) 2001-06-15 2009-02-17 Cardiac Pacemakers, Inc. Pulmonary vein stent for treating atrial fibrillation
US7340303B2 (en) 2001-09-25 2008-03-04 Cardiac Pacemakers, Inc. Evoked response sensing for ischemia detection
US6973349B2 (en) 2001-12-05 2005-12-06 Cardiac Pacemakers, Inc. Method and apparatus for minimizing post-infarct ventricular remodeling
US7072711B2 (en) 2002-11-12 2006-07-04 Cardiac Pacemakers, Inc. Implantable device for delivering cardiac drug therapy
US7627373B2 (en) 2002-11-30 2009-12-01 Cardiac Pacemakers, Inc. Method and apparatus for cell and electrical therapy of living tissue
US7320675B2 (en) 2003-08-21 2008-01-22 Cardiac Pacemakers, Inc. Method and apparatus for modulating cellular metabolism during post-ischemia or heart failure
US7215997B2 (en) 2003-12-22 2007-05-08 Cardiac Pacemakers, Inc. Dynamic device therapy control for treating post myocardial infarction patients
US7840263B2 (en) 2004-02-27 2010-11-23 Cardiac Pacemakers, Inc. Method and apparatus for device controlled gene expression
US7764995B2 (en) 2004-06-07 2010-07-27 Cardiac Pacemakers, Inc. Method and apparatus to modulate cellular regeneration post myocardial infarct
US7567841B2 (en) 2004-08-20 2009-07-28 Cardiac Pacemakers, Inc. Method and apparatus for delivering combined electrical and drug therapies
US7981065B2 (en) 2004-12-20 2011-07-19 Cardiac Pacemakers, Inc. Lead electrode incorporating extracellular matrix
US8060219B2 (en) 2004-12-20 2011-11-15 Cardiac Pacemakers, Inc. Epicardial patch including isolated extracellular matrix with pacing electrodes
US7616990B2 (en) 2005-10-24 2009-11-10 Cardiac Pacemakers, Inc. Implantable and rechargeable neural stimulator

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US2461990A (en) * 1947-06-07 1949-02-15 Wingfoot Corp Polymers and copolymers of propiolates
US2898327A (en) * 1956-04-18 1959-08-04 Exxon Research Engineering Co Polymerization of olefins
US3159608A (en) * 1963-01-08 1964-12-01 Exxon Research Engineering Co Copolymerization of ethylene and vinyl acetate
US3271378A (en) * 1963-11-08 1966-09-06 Gen Aniline & Film Corp Process of polymerizing acetylene and derivatives thereof
US3389979A (en) * 1964-06-03 1968-06-25 Exxon Research Engineering Co Middle distillate flow improver
US3567639A (en) * 1966-06-01 1971-03-02 Exxon Research Engineering Co Hydrocarbon-containing compositions
US4048411A (en) * 1975-05-31 1977-09-13 Basf Aktiengesellschaft Manufacture of copolymers of ethylene
US4074040A (en) * 1976-03-18 1978-02-14 Basf Aktiengesellschaft Manufacture of ethylene polymers in an autoclave reactor
US4076919A (en) * 1975-12-20 1978-02-28 Basf Aktiengesellschaft Manufacture of ethylene polymers in a two-zone tubular reactor at pressure above 500 bars
US4087601A (en) * 1976-04-21 1978-05-02 Basf Aktiengesellschaft Manufacture of ethylene/n-butyl acrylate copolymers
US4093795A (en) * 1975-06-03 1978-06-06 Basf Aktiengesellschaft Multi-stage isolation of high pressure polyethylene
US4169929A (en) * 1977-05-16 1979-10-02 Basf Aktiengesellschaft Manufacture of low density ethylene polymers of improved homogeneity
US4217431A (en) * 1978-01-24 1980-08-12 Basf Aktiengesellschaft Manufacture of ethylene copolymers

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DE2044655C3 (de) * 1970-09-09 1979-05-10 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Copolymerisaten des Äthylens

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2192931A (en) * 1940-03-12 acetylene
US2461990A (en) * 1947-06-07 1949-02-15 Wingfoot Corp Polymers and copolymers of propiolates
US2898327A (en) * 1956-04-18 1959-08-04 Exxon Research Engineering Co Polymerization of olefins
US3159608A (en) * 1963-01-08 1964-12-01 Exxon Research Engineering Co Copolymerization of ethylene and vinyl acetate
US3271378A (en) * 1963-11-08 1966-09-06 Gen Aniline & Film Corp Process of polymerizing acetylene and derivatives thereof
US3389979A (en) * 1964-06-03 1968-06-25 Exxon Research Engineering Co Middle distillate flow improver
US3567639A (en) * 1966-06-01 1971-03-02 Exxon Research Engineering Co Hydrocarbon-containing compositions
US4048411A (en) * 1975-05-31 1977-09-13 Basf Aktiengesellschaft Manufacture of copolymers of ethylene
US4093795A (en) * 1975-06-03 1978-06-06 Basf Aktiengesellschaft Multi-stage isolation of high pressure polyethylene
US4076919A (en) * 1975-12-20 1978-02-28 Basf Aktiengesellschaft Manufacture of ethylene polymers in a two-zone tubular reactor at pressure above 500 bars
US4074040A (en) * 1976-03-18 1978-02-14 Basf Aktiengesellschaft Manufacture of ethylene polymers in an autoclave reactor
US4087601A (en) * 1976-04-21 1978-05-02 Basf Aktiengesellschaft Manufacture of ethylene/n-butyl acrylate copolymers
US4169929A (en) * 1977-05-16 1979-10-02 Basf Aktiengesellschaft Manufacture of low density ethylene polymers of improved homogeneity
US4217431A (en) * 1978-01-24 1980-08-12 Basf Aktiengesellschaft Manufacture of ethylene copolymers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532270A (en) * 1984-01-27 1985-07-30 National Starch And Chemical Corporation High temperature stable adhesive compositions employing aromatic polyimide and polyisoimide bis-acetylene additives
US5559191A (en) * 1994-08-30 1996-09-24 Bp Chemicals Limited Functionalised hydrocarbyl polymers
US20040002739A1 (en) * 2002-06-28 2004-01-01 Cates Adam W. Method and apparatus for delivering pre-shock defibrillation therapy
US7089055B2 (en) 2002-06-28 2006-08-08 Cardiac Pacemakers, Inc. Method and apparatus for delivering pre-shock defibrillation therapy

Also Published As

Publication number Publication date
EP0054138A1 (de) 1982-06-23
JPS57121011A (en) 1982-07-28
DE3164597D1 (en) 1984-08-09
CA1222348A (en) 1987-05-26
DE3046802A1 (de) 1982-07-15
EP0054138B1 (de) 1984-07-04

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